CN102491459A - 一种非金属掺杂钛基薄膜电极、制备方法及其应用 - Google Patents
一种非金属掺杂钛基薄膜电极、制备方法及其应用 Download PDFInfo
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Abstract
一种非金属掺杂钛基薄膜电极、制备方法及其应用,属于无机非金属材料的光电催化技术领域。包括以下步骤:将非金属元素的单质或化合物与异丙醇钛混合反应制备非金属掺杂TiO2颗粒,制备TiO2纳晶,将非金属掺杂TiO2颗粒、造孔剂与TiO2纳晶乳状液混合制备成胶乳并涂膜,然后进行热处理即可。本发明所制备的非金属掺杂钛基薄膜电极用于光电催化降解水中污染物如染料、酚类、醛类、药物或重金属离子。本发明的电极具有可见光响应、大的比表面积、与基底粘附力强等优势。
Description
技术领域
本发明属于无机非金属材料的光电催化技术领域,具体涉及一种应用于光电催化的非金属掺杂钛基薄膜电极、制备方法及其应用。
背景技术
目前,常用的废水中有害物质去除技术一般包括物理吸附法、混凝法、气浮法等。这些方法是将有机污染物从液相转移到固相,从而会造成二次污染和吸附剂、混凝剂再生等一系列新的环境问题。一般的化学、生化等处理技术虽能分解有机污染物质,但除净度低,处理后废水无法达到国家废水排放标准。1972年日本fujishima等(Fujishima A.,Honda K.Electrochemical photolysis ofwater at a semiconductor electrode,Nature,1972,328:37-38.)报道了TiO2电极上发生了光电解水现象以来,TiO2以其活性高,热稳定性好,抗光氧化性强,价格便宜等特性备受瞩目。近年来,电化学辅助TiO2光催化技术被广泛关注。它的优点是外加电压使光激发产生的光生电子通过外电路被驱赶到对电极上,阻止了光生电子和光生空穴的复合,从而提高了光催化的效率;将TiO2固定化,避免了悬浮态反应体系纳米催化剂颗粒与溶液的分离,同时保留了TiO2的纳米尺寸效应。光电极是光电催化反应器的关键部件,因此制备具有良好光催化性能、尤其是具有可见光催化活性的TiO2薄膜电极成为目前光催化技术研究的热点之一。
可见光占太阳光谱的41%,为了增强TiO2薄膜电极的可见光响应能力,提高对太阳光的利用率,人们采取了掺杂、表面贵金属修饰、半导体复合等手段对TiO2薄膜电极进行修饰。Kunpeng等(Kunpeng X.,Lan S.,Chenglin W.,et al.Electrochimica Acta 2010,55:7211-7218.)用脉冲电流沉积法制备了负载Ag的TiO2阵列薄膜电极,显示了较高的光电催化性能。Lei等(Lei H.,Yanjun X.,Huiling L.,et al.J.Hazard.Mater.2010,175:524-531.)通过等离子体基离子注入法制备了N掺杂的TiO2/Ti纳米阵列并应用于可见光激发的光电催化降解。但是,通过涂覆法将非金属掺杂的TiO2覆盖在导电基底上制备用于光电催化降解的薄膜电极的方法还未见报道。
发明内容
本发明的目的在于提供用于光电催化降解的非金属掺杂钛基薄膜电极制备方法。本发明方法简单易行,可控性和重复性好。
本发明所提供的非金属掺杂钛基薄膜电极的制备方法,具体步骤如下:
1)非金属掺杂TiO2颗粒的制备:将非金属元素的单质或化合物与异丙醇钛超声混合,所得混合溶液中掺杂的非金属元素的单质或化合物与钛摩尔比为0.01~0.3∶1;在空气条件下,将所得混合物10~100℃恒温持续搅拌24~48小时直到混合物成为粉末状态;之后将粉末置于马弗炉中200~600℃焙烧1~6小时,即得到纳微尺寸的非金属掺杂TiO2颗粒;
2)TiO2纳晶乳状液体的制备:在持续搅拌中,将乙酸滴入异丙醇钛中,10~60分钟后倒入去离子水中加热至50~200℃并持续搅拌10~60分钟,加入硝酸调节pH值至4~1,再于100~250℃加热2~20小时,得到TiO2纳晶的乳状液体,其中,TiO2的固含量为5~30%;
3)非金属掺杂TiO2薄膜电极的制备:步骤1)制备的非金属掺杂TiO2颗粒、造孔剂与步骤(2)所得TiO2纳晶的乳状液体混合并研磨分散均匀后,加入溶剂调节浓度,得到TiO2的总固含量为5~30%的浆料;通过涂覆法将浆料均匀涂敷在导电基底上并在室温下干燥,之后将薄膜在50~600℃下进行热处理0.2~3小时,得到非金属掺杂钛基薄膜电极。
其中,所述的非金属元素的单质或化合物包括:葡萄糖、蔗糖;碘单质,碘化钾、碘化钠等碘盐;氯化钾、氯化钠等氯盐;溴化钾、溴化钠等溴盐;硫化钠、硫化钾等硫化物。加入葡萄糖、蔗糖得到的是掺杂碳的TiO2颗粒,加入碘单质,碘化钾、碘化钠等碘盐得到的是掺杂碘的TiO2颗粒,加入氯化钾、氯化钠等氯盐的得到的是掺杂氯的TiO2颗粒,加入溴化钾、溴化钠等溴盐的得到的是掺杂溴的TiO2颗粒,加入硫化钠、硫化钾等硫化物的得到的是掺杂硫的TiO2颗粒。
所述的造孔剂包括聚乙二醇、纤维素钠。
所述溶剂为无水乙醇、去离子水或无水乙醇与去离子水的混合溶液。
所述导电基底为FTO导电玻璃、ITO导电玻璃、柔性导电基底、铂片、铝片、铁片。
本发明所制备的非金属掺杂钛基薄膜电极用于光电催化降解水中污染物的其中,所述的污染物包括染料、酚类、醛类、药物或重金属离子。具体可采用以下步骤:
用本发明制备的非金属掺杂钛基薄膜电极作工作电极,铂片作对电极,标准甘汞电极作参比电极,将三个电极浸泡在0.1~1mol/L的电解液中构建一个三电极体系。将降解物溶解到电解液中,配制成浓度为10-3~10-6mol/L的目标降解物溶液,搅拌使目标降解物在薄膜电极表面达到吸附-脱附平衡。之后,对薄膜进行光照,同时外加0.1~1V电压,在固定时间间隔内取样分析,观察溶液中目标降解物的浓度变化。
所述的光源包括可见光源、模拟太阳光源及太阳光。
所述的电解液包括Na2SO4、KOH、NaCl等盐溶液。
与现有技术相比较,本发明具有以下优点:
1)本发明所提供的方法简单易操作,可控性和重复性强,适用于工业化生产。
2)本发明所提供的非金属掺杂钛基薄膜电极具有可见光响应、大的比表面积、与基底粘附力强等优势。实验表明,由该发明方法制备的非金属掺杂钛基薄膜电极具有高的光电催化效率。
附图说明
图1、实施例1制备的碳掺杂TiO2颗粒的扫描电镜图;
图2、实施例1、实施例2和对比例1中制备的碳掺杂、碘掺杂TiO2和无掺杂的薄膜电极的紫外可见漫反射谱图;
图3、实施例3中薄膜电极光电催化降解罗丹明B的降解动力学曲线。
以下结合附图和实例来对本发明作进一步说明。
具体实施方式
实施例1
1)碳掺杂TiO2颗粒的制备:将葡萄糖与异丙醇钛按照碳与钛摩尔比为0.05∶1的比例超声混合,在空气条件下,所得混合溶液30℃水浴恒温持续搅拌48小时直到混合物成为粉末状态。之后将粉末置于马弗炉中400℃焙烧4小时,即得到碳掺杂TiO2颗粒;
2)TiO2纳晶的制备:在500转/分钟的搅拌转速下,将4mL乙酸滴入40mL异丙醇钛中后,持续搅拌20分钟,而后匀速加入水中加热至80℃并持续搅拌30分钟。加入硝酸调节pH值至3,再于180℃加热12小时,得到TiO2纳晶的乳状液体,其中,TiO2的固含量为20%;
3)碳掺杂钛基薄膜电极的制备:0.5g碳掺杂TiO2颗粒、0.02g聚乙二醇20000与1g TiO2纳晶的乳状液体混合并研磨分散均匀后,加入乙醇调节浓度,得到TiO2的总固含量为10%的浆料。通过手术刀刮涂法将浆料均匀涂敷在ITO导电玻璃基底上并在室温下干燥,之后将薄膜在500℃下进行热处理1小时,得到碳掺杂钛基薄膜电极。
如图1,薄膜中颗粒分布均匀,没有大块聚集现象。薄膜没有大的裂痕,与基底结合牢固。
实施例2
1)碘掺杂TiO2颗粒的制备:将单质碘与异丙醇钛按照碘与钛摩尔比为0.1∶1的比例超声混合,在空气条件下,所得混合溶液30℃水浴恒温持续搅拌48小时直到混合物成为粉末状态。之后将粉末置于马弗炉中500℃焙烧3小时,即得碘掺杂TiO2颗粒;
2)同实施例1步骤2)
3)碘掺杂钛基薄膜电极的制备:0.5g碘掺杂TiO2颗粒、0.01g聚乙二醇20000与1g TiO2纳晶的乳状液体混合并研磨分散均匀后,加入去离子水调节浓度,得到TiO2的总固含量为15%的浆料。通过手术刀刮涂法、将浆料均匀涂敷在ITO导电玻璃基底上并在室温下干燥,之后将薄膜在400℃下进行热处理1小时,得到碘掺杂钛基薄膜电极。
实施例3
1)氯掺杂TiO2颗粒的制备:将氯化钾与异丙醇钛按照氯与钛摩尔比为0.15∶1的比例超声混合,所得混合溶液在与空气接触的条件下,50℃水浴恒温持续搅拌48小时直到混合物成为粉末状态。之后将粉末置于马弗炉中550℃焙烧2小时,即得氯掺杂TiO2颗粒;
2)同实施例1步骤2)
3)氯掺杂钛基薄膜电极的制备:0.5g氯掺杂TiO2颗粒、0.01g纤维素钠与1g TiO2纳晶的乳状液体混合并研磨分散均匀后,加入去离子水调节浓度,得到TiO2的总固含量为20%的浆料。通过手术刀刮涂法、将浆料均匀涂敷在ITO导电玻璃基底上并在室温下干燥,之后将薄膜在500℃下进行热处理2小时,得到氯掺杂钛基薄膜电极。
对比例1
1)纯TiO2颗粒的制备:异丙醇钛在与空气充分接触的条件下,30℃水浴恒温持续搅拌48小时直到混合物成为粉末状态。之后将粉末置于马弗炉中600℃焙烧5小时,即得到纯TiO2颗粒;
2)纯TiO2薄膜电极的制备:0.5g纯TiO2颗粒、0.02g聚乙二醇20000与1g TiO2纳晶的乳状液体混合并研磨分散均匀后,加入溶剂调节浓度,得到TiO2的总固含量为15%的浆料。通过手术刀刮涂法、将浆料均匀涂敷在ITO导电玻璃基底上并在室温下干燥,之后将薄膜在500℃下进行热处理1小时,得到纯TiO2薄膜电极。
焙烧后的纯TiO2薄膜为白色,而实施例1中制备的碳掺杂TiO2薄膜为灰白色,实施例2中制备的碘掺杂TiO2薄膜为黄褐色。
如图2,对比纯TiO2薄膜与碳掺杂和碘掺杂TiO2薄膜的紫外吸收光谱,可以看出掺杂后出现了明显的红移现象,即在可见光区有光电响应。并且,碘掺杂的薄膜红移程度大于碳掺杂薄膜。
实施例4
光电催化降解水中罗丹明B:用实施例1、实施例2和对比例1中制备的碳掺杂、碘掺杂和纯的TiO2薄膜作工作电极,铂片作对电极,标准甘汞电极作参比电极,将三个电极浸泡在0.5mol/L的Na2SO4溶液中构建一个三电极反应体系。将一定质量的罗丹明B溶解到Na2SO4溶液中,配制成浓度为5×10-6mol/L的溶液,搅拌30分钟,使罗丹明B在薄膜电极表面达到吸附-脱附平衡。之后,对薄膜电极进行可见光照,同时外加0.5V电压,每隔1小时取样分析,观察溶液中罗丹明B的浓度变化。
如图3,可以看出光电催化降解速率遵循纯二氧化钛薄膜电极<碳掺杂二氧化钛薄膜电极<碘掺杂二氧化钛薄膜电极的顺序,即掺杂后,薄膜电极的光电催化降解速率明显增加。
Claims (7)
1.一种非金属掺杂钛基薄膜电极的制备方法,其特征在于,包括以下步骤:
1)非金属掺杂TiO2颗粒的制备:将非金属元素的单质或化合物与异丙醇钛超声混合,所得混合溶液中掺杂的非金属元素的单质或化合物与钛摩尔比为0.01~0.3∶1;在空气条件下,将所得混合物10~100℃恒温持续搅拌24~48小时直到混合物成为粉末状态;之后将粉末置于马弗炉中200~600℃焙烧1~6小时,即得到纳微尺寸的非金属掺杂TiO2颗粒;
2)TiO2纳晶乳状液体的制备:在持续搅拌中,将乙酸滴入异丙醇钛中,10~60分钟后倒入去离子水中加热至50~200℃并持续搅拌10~60分钟,加入硝酸调节pH值至4~1,再于100~250℃加热2~20小时,得到TiO2纳晶的乳状液体,其中,TiO2的固含量为5~30%;
3)非金属掺杂TiO2薄膜电极的制备:步骤1)制备的非金属掺杂TiO2颗粒、造孔剂与步骤(2)所得TiO2纳晶的乳状液体混合并研磨分散均匀后,加入溶剂调节浓度,得到TiO2的总固含量为5~30%的浆料;通过涂覆法将浆料均匀涂敷在导电基底上并在室温下干燥,之后将薄膜在50~600℃下进行热处理0.2~3小时,得到非金属掺杂钛基薄膜电极。
2.按照权利要求1所述的方法,其特征在于,所述的非金属元素的单质或化合物为葡萄糖、蔗糖、碘单质、碘盐、溴盐、氯盐、硫化物。
3.按照权利要求1所述的方法,其特征在于,所述的造孔剂包括聚乙二醇、纤维素钠。
4.按照权利要求1所述的方法,其特征在于,所述溶剂为无水乙醇、去离子水或无水乙醇与去离子水的混合溶液。
5.按照权利要求1所述的方法,其特征在于,所述导电基底为FTO导电玻璃、ITO导电玻璃、柔性导电基底、铂片、铝片或铁片。
6.权利要求1-5所述的任一方法所制备的非金属掺杂钛基薄膜电极。
7.权利要求6的任一非金属掺杂钛基薄膜电极用于光电催化降解水中污染物,所述的污染物包括染料、酚类、醛类、药物或重金属离子。
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